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US4476297A - Process for removing catalyst residues from polyolefins - Google Patents

Process for removing catalyst residues from polyolefins Download PDF

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Publication number
US4476297A
US4476297A US06/407,123 US40712382A US4476297A US 4476297 A US4476297 A US 4476297A US 40712382 A US40712382 A US 40712382A US 4476297 A US4476297 A US 4476297A
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United States
Prior art keywords
catalyst
titanium
acid
aluminum
added
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Expired - Fee Related
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US06/407,123
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English (en)
Inventor
Hans-Jurgen Kablitz
Helmut Strametz
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Hoechst AG
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Hoechst AG
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Assigned to HOECHST AKTIENGESELLSCHAFT reassignment HOECHST AKTIENGESELLSCHAFT ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: KABLITZ, HANS-JURGEN, STRAMETZ, HELMUT
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F6/00—Post-polymerisation treatments
    • C08F6/02—Neutralisation of the polymerisation mass, e.g. killing the catalyst also removal of catalyst residues

Definitions

  • the present invention relates to a process for removing catalyst residues from polyolefins prepared with the use of mixed catalysts containing light metal halides and titanium and aluminum compounds.
  • catalyst systems are used, the transition metal component of which contains relatively large amounts of magnesium chloride, or another magnesium halide, and, under certain circumstances, also halides of aluminum and of alkali and alkaline earth metals.
  • the polymerization activity of such a system can be very high, so that it is possible to prepare polyolefins which contain only small amounts of catalyst residues. For many areas of use it is therefore possible to omit a purification step to remove catalyst residues from the polymers.
  • some applications of polyolefins require extremely low amounts of contaminants.
  • polypropylene prepared with the use of catalysts containing magnesium chloride can be purified by adding an aliphatic alcohol having 3 to 8 carbon atoms to a suspension of the polymer in an inert hydrocarbon (cf. German Offenlegungsschrift No. 2,436,989).
  • a first treatment step with the exclusion of water and alcohols it is also possible to use aliphatic monocarboxylic acids having 1 to 3 carbon atoms, while the use of higher carboxylic acids having more than 3 carbon atoms is considered unfavorable (c.f. Japanese Preliminary Published Application No. Sho 52/49,285).
  • the treatment can be carried out in a suspension in an inert diluent, in the gas phase or in the melt.
  • water, alkalis, inert gas or vacuum can be used for aftertreating.
  • a purification process for removing magnesium chloride from polyolefins is also known, the process being carried out with the aid of aromatic monocarboxylic acids, polycarboxylic acids or hydroxycarboxylic acids, preferably aliphatic polycarboxylic acids having 2 to 6 carbon atoms, and in the melt with the exclusion of water (c.f. Japanese Preliminary Published Application No. Sho 52/69,488).
  • glycol monoethers to remove magnesium chloride from polypropylene is also known (cf. Japanese Preliminary Published Application No. Sho 54/142,290).
  • additives described above for the purification of polypropylene, are that their effectiveness in respect of the removal of light metal halides, in particular magnesium chloride, leaves something to be desired. Either large amounts of several percent by weight of the corresponding chemicals must be added, or very high temperatures or even several treatment steps are necessary to obtain the purification effect desired.
  • Additives having a low boiling point also have the additional disadvantage that they can become concentrated in the unconverted monomer or in the inert diluent. Certain of these materials also tend to react in an unclear manner with the catalyst constituents, so that there is a resulting profusion of by-products, which can contaminate the excess monomer and the diluent and be separated off only with difficulty.
  • the invention thus relates to a process for removing catalyst residues from polyolefins prepared by means of catalysts containing light metal halides and titanium and aluminum compounds by treating the polyolefin suspended in a liquid medium, with an aliphatic monocarboxylic acid and separating off and washing out the polyolefin, which process comprises carrying out this treatment with 0.1 to 1.5% by weight relative to dry polyolefin, of at least one monocarboxylic acid having 6 to 10 carbon atoms at a temperature of 40° to 90° C. for 10 to 120 minutes.
  • the process according to the invention is suitable for all homopolymers and copolymers of ethylene, propylene and higher 1-olefins prepared with the use of catalyst systems which, in addition to titanium halides, predominantly contain light metal halides, in particular magnesium halides, and aluminum alkyl compounds.
  • the process is carried out in a liquid medium, advantageously directly after the polymerization of the olefin. If the polymerization took place in a suspension, either in liquid monomer or in an inert diluent, the suspension, if necessary, can be diluted with a low-boiling diluent. If, on the other hand, the polymerization took place in the gas phase, in which the polymer is obtained as a powder, a suspension of the polymer in a low-boiling diluent, for example a butane, pentane or hexane fraction, is prepared.
  • a low-boiling diluent for example a butane, pentane or hexane fraction
  • the treatment of the polymer is carried out at a temperature of 40° to 90° C., preferably 60° to 75° C.
  • the treatment time depends on the porosity and particle size distribution of the polymer particles and is within the range from 10 to 120 minutes, preferably 30 to 60 minutes.
  • the amount of treatment agent is related to the productivity of the catalyst component containing titanium halide and light metal halide and with the amount of aluminum alkyl compound used as co-catalyst and is within the range from 0.1 to 1.5% by weight, preferably 0.2 to 0.5% by weight, relative to dry polymer.
  • the process can be carried out not only discontinuously but also continuously. It is particularly advantageous when the treatment agent acts on the polymer in a countercurrent wash.
  • the polymer suspension is introduced into a washing tower provided with a stirrer and baffles, the liquid phase containing the treatment agent moving upwards while the polymer particles sink to the bottom.
  • the catalyst residues can also be removed in a stirred vessel or in two or more units connected in series.
  • the treatment agent used is at least one aliphatic, preferably branched, monocarboxylic acid having 6 to 10, preferably 7 to 9 carbon atoms.
  • aliphatic, preferably branched, monocarboxylic acid having 6 to 10, preferably 7 to 9 carbon atoms.
  • Examples of such acids are
  • n-hexanoic acid (caproic acid), isobutylacetic acid, sec.-butylacetic acid, diethylacetic acid, methyl-n-propylacetic acid, methyl-i-propylacetic acid, dimethylethylacetic acid,
  • n-heptanoic acid (oenanthic acid), methylbutylacetic acid, ethyl-n-propylacetic acid, methyldiethylacetic acid,
  • n-octanoic acid caprylic acid
  • 2-ethylhexanoic acid i-octanoic acid
  • isomeric nonanoic acids isomeric decanoic acids.
  • products or product mixtures obtained by hydroformylation from higher monoolefins and subsequent oxidation are used. These are, for example in the case of i-octanoic acid (IOA) and i-nonanoic acid (INA), which are preferably used, mixtures of isomeric C 8 - or C 9 -carboxylic acids.
  • 2-Ethylhexanoic acid (2-EHA) is particularly preferred.
  • the acids can be used in pure form or mixed.
  • the process according to the invention can be applied to any system obtained with the aid of a magnesium- and titanium-containing catalyst component A and a co-catalyst B containing an aluminum alkyl compound.
  • Component A of this catalyst can be prepared, for example, by reacting the reaction product of a magnesium halide and an electron donor and/or of a cyclopolyene with the reaction product of titanium tetrachloride with an aluminum-organic compound at temperatures of -50° to +80° C. (cf., for example, German Offenlegungsschrift No. 2,830,039).
  • the component can also be prepared by reacting the reaction product of a magnesium halide and an electron donor compound with titanium tetrachloride (c.f. German Offenlegungsschrift No. 2,643,143) by reacting magnesium ethylate with titanium tetrachloride (c.f., for example, German Auslegeschrift No. 1,795,197).
  • Another possibility comprises reacting a magnesium halide with a reaction product of titanium tetrachloride with an electron donor (c.f., for example, German Offenlegungsschrift No. 2,230,672).
  • the reactions of the magnesium halide with the various additives are generally effected by milling. It is possible in these reactions, if desired, to add to the magnesium halide yet other inorganic compounds which can later be partially removed likewise by the process according to the invention, such as LiCl, Na 2 SO 4 , CaCl 2 , CaCO 3 , CaSO 4 , MgO, AlCl 3 , Al 2 O 3 , SiO 2 or TiO 2 . It is also possible simultaneously or successively to use several electron donor compounds, which in turn can also form complexes, for example with AlCl 3 or TiCl 4 .
  • Co-catalyst B can be comprised of an aluminum alkyl compound of the formula AlR 3 or AlR 2 Hal, where R can be a straight-chain or branched alkyl radical and Hal can be a chloride or bromide radical.
  • R can be a straight-chain or branched alkyl radical and Hal can be a chloride or bromide radical.
  • the compounds aluminum triethyl, aluminum triisobutyl and aluminum diethyl chloride are preferably used.
  • reaction products of aluminum triisobutyl and of aluminum diisobutyl hydride with dienes for example isoprene
  • the latter reaction product is commercially available as aluminum isoprenyl.
  • the aluminum alkyl compound is as a rule used in the form of a complex with an electron donor compound.
  • Esters of carboxylic acids are particularly suitable for this use.
  • ethers, thioethers, nitrogen and phosphorus compounds and cyclopolyenes can also be used, either singly or as mixtures.
  • the electron donor compound can also be metered separately from the co-catalyst as component C directly into the polymerization mixture.
  • the process according to the invention can be used for removing the residues of any catalyst system of the abovementioned type, regardless of whether these catalyst systems are used for preparing a homopolymer or a random or block copolymer.
  • the process is particularly effective in the case of any homopolymers and copolymers of propylene. Its application reduces above all the content of aluminum, magnesium, titanium and chloride.
  • the low-ash products thereby obtained can be used with great advantage for preparing films and cable sheaths having high breakdown resistance and a low dielectric loss factor. The corrosive action of the products on processing machines is considerably reduced.
  • a TiCl 3 -containing catalyst component A which had been prepared in accordance with Example 1 of German Offenlegungsschrift No. 2,830,039 was used for the polymerization of propylene.
  • 1,090 ml of a hydrogenated, oxygen-free gasoline fraction (boiling point 130° to 170° C.) and 550 ml of titanium tetrachloride (5 moles) were initially introduced into a 10 liter stirred vessel with the exclusion of air and moisture.
  • a solution of 1,111.2 g of aluminum ethyl sesquichloride (which contains 4.5 moles of aluminum diethyl monochloride) in 3,334 g of the same gasoline fraction is added dropwise with stirring (250 rpm) at 0° C. in the course of 8 hours under a blanket of nitrogen. A red-brown fine precipitate formed. Stirring was then continued for 2 hours at 0° C. and then for 12 hours at room temperature.
  • the batch was then heated with stirring and under a blanket of nitrogen for 4 hours at 60° C. After the mixture had cooled down and the precipitate had settled out, the supernatent mother liquor was decanted off, and the solid reaction product was washed three times with 2,000 ml of the gasoline fraction in each case. For the subsequent reactions, the solid was suspended in an amount of the gasoline fraction which was such that a concentration of 1 mole of TiCl 3 per 1 liter was obtained. The content of trivalent titanium in the suspension was determined by titration with a Ce III solution.
  • the yield was 5.84 kg, which corresponds to 122 kg of PP per g of Ti, from which the amount of 2-ethylhexanoic acid added can be calculated to be 0.2% by weight.
  • the polymer had a bulk density of 460 g/l and an indentation hardness, measured according to DIN 53,456, of 84 N/mm 2 .
  • 2.4% by weight of soluble (atactic) polypropylene (relative to total polymer) were formed. Analytically determined residual contents of catalyst constitutents are indicated in Table 1.
  • Example 1 The polymerization according to Example 1 was repeated several times, the amounts of 2-ethylhexanoic acid added being increased in a stepwise manner and the treatment temperature being changed.
  • the experimental results correspond to Example 1 with the exception of the results listed in Table 1.
  • Example 2 Further polymerizations in accordance with Example 1 were carried out, followed by the addition of i-octanoic acid (IOA) or of i-nonanoic acid (INA) to remove the catalyst residues. The reduction obtained in these residues in relation to the catalyst yield is shown in Table 2.
  • IOA i-octanoic acid
  • INA i-nonanoic acid
  • the polymerization is carried out in accordance with Example 1, but without a subsequent removal of the catalyst residues being carried out.
  • the content of these residues in the polymer in relation to the catalyst yield is indicated in Table 1.
  • a titanium-containing catalyst component A was used which had been prepared in line with Example 1 of German Offenlegungsschrift No. 2,643,143 as follows:
  • the catalyst component A prepared in accordance with Example 6 and containing titanium was used. 35 liters of liquid propylene and 0.4 bar of hydrogen were initially introduced at room temperature with the exclusion of air and moisture into a 70 liter stirred autoclave, and the catalyst components, each diluted with 5 liters of liquid propylene, were added from a lock vessel in the following order and the following amounts:
  • acetic acid (EA) was added in two different concentrations (c.f. Table 2). Even at a high concentration, no good removal of catalyst residues was obtained.
  • the precipitate was then washed six times, each time with the addition of 3 liters of the gasoline fraction, 15 minutes' stirring, settling out of the solids and decanting off of the supernatant mother liquor.
  • the gasoline fraction above the solid should be free of titanium compound.
  • the volume of the suspension was made up to 5 liters.
  • the titanium content of the suspension was determined by colorimetry after the addition of H 2 O 2 .
  • 10 ml of the suspension contained 2.1 mmoles of titanium compound.
  • 100 liters of a gasoline fraction (boiling range 130° to 170° C.) were initially introduced at room temperature into a 150 liter stirred vessel with the exclusion of air and moisture.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Catalysts (AREA)
US06/407,123 1981-08-21 1982-08-11 Process for removing catalyst residues from polyolefins Expired - Fee Related US4476297A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19813133101 DE3133101A1 (de) 1981-08-21 1981-08-21 Verfahren zur entfernung von katalysatorresten aus polyolefinen
DE3133101 1981-08-21

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US (1) US4476297A (es)
EP (1) EP0073001B1 (es)
AR (1) AR227485A1 (es)
AU (1) AU554147B2 (es)
BR (1) BR8204906A (es)
CA (1) CA1190347A (es)
DE (2) DE3133101A1 (es)
ES (1) ES8308896A1 (es)
ZA (1) ZA826056B (es)

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4701504A (en) * 1986-01-23 1987-10-20 Du Pont Canada Inc. Reduction of isomerization in solution process for polymerization of alpha-olefins
US4704421A (en) * 1985-08-06 1987-11-03 El Paso Products Company Nucleation of propylene polymers
EP0316982A3 (en) * 1987-10-29 1990-02-21 Shell Internationale Research Maatschappij B.V. Method for separating metal contaminants from organic polymers
US5011739A (en) * 1989-10-02 1991-04-30 Eastman Kodak Company Moisture stable biasable transfer members and method for making same
US5196630A (en) * 1991-04-25 1993-03-23 Mobil Oil Corporation Process for the removal of catalyst residues from olefin polymerization products
US5212032A (en) * 1991-11-26 1993-05-18 Eastman Kodak Company Moisture stable polyurethane biasable transfer members
US5217838A (en) * 1991-11-26 1993-06-08 Eastman Kodak Company Moisture stable biasable transfer members
US5250357A (en) * 1991-11-26 1993-10-05 Eastman Kodak Company Moisture stable elastomeric polyurethane biasable transfer members
US6458919B1 (en) * 1993-02-12 2002-10-01 Ticona Gmbh Fibers made of cycloolefin copolymers
US20050101761A1 (en) * 2003-11-12 2005-05-12 Lambert Timothy L. Process for removal of catalyst residues from poly-alpha-olefins
US20100069687A1 (en) * 2006-09-06 2010-03-18 Chemtura Corporation Process for synthesis of polyalphaolefin and removal of residual catalyst components
EP2395028A1 (en) 2006-09-06 2011-12-14 Chemtura Corporation Process for removal of residual catalyst components
US20160237239A1 (en) * 2015-02-16 2016-08-18 Fina Technology, Inc. Polymer foams
US10562973B2 (en) 2014-04-08 2020-02-18 Prothena Bioscience Limited Blood-brain barrier shuttles containing antibodies recognizing alpha-synuclein

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5017685A (en) * 1989-02-24 1991-05-21 E. I. Du Pont De Nemours And Company Process for extracting metal residue from poly(ether ketone ketones)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2827445A (en) * 1955-09-16 1958-03-18 Dow Chemical Co Purification of polymerized olefins prepared with catalytic metal compounds
FR1363804A (fr) * 1962-07-26 1964-06-12 Du Pont Procédé de récupération des polyoléfines
US3269997A (en) * 1955-04-06 1966-08-30 Phillips Petroleum Co Process for production and recovery of polymers
US3287343A (en) * 1963-12-10 1966-11-22 Hercules Inc Purification of polyolefins
US3499880A (en) * 1966-01-18 1970-03-10 Hercules Inc Purification of polyolefins using alkanoic acids

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3269997A (en) * 1955-04-06 1966-08-30 Phillips Petroleum Co Process for production and recovery of polymers
US2827445A (en) * 1955-09-16 1958-03-18 Dow Chemical Co Purification of polymerized olefins prepared with catalytic metal compounds
FR1363804A (fr) * 1962-07-26 1964-06-12 Du Pont Procédé de récupération des polyoléfines
US3164578A (en) * 1962-07-26 1965-01-05 Du Pont Recovery process for polyolefins
US3287343A (en) * 1963-12-10 1966-11-22 Hercules Inc Purification of polyolefins
US3499880A (en) * 1966-01-18 1970-03-10 Hercules Inc Purification of polyolefins using alkanoic acids

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4704421A (en) * 1985-08-06 1987-11-03 El Paso Products Company Nucleation of propylene polymers
US4701504A (en) * 1986-01-23 1987-10-20 Du Pont Canada Inc. Reduction of isomerization in solution process for polymerization of alpha-olefins
EP0316982A3 (en) * 1987-10-29 1990-02-21 Shell Internationale Research Maatschappij B.V. Method for separating metal contaminants from organic polymers
US4992529A (en) * 1987-10-29 1991-02-12 Shell Oil Company Method for separating metal contaminants from organic polymers
US5011739A (en) * 1989-10-02 1991-04-30 Eastman Kodak Company Moisture stable biasable transfer members and method for making same
US5196630A (en) * 1991-04-25 1993-03-23 Mobil Oil Corporation Process for the removal of catalyst residues from olefin polymerization products
US5250357A (en) * 1991-11-26 1993-10-05 Eastman Kodak Company Moisture stable elastomeric polyurethane biasable transfer members
US5217838A (en) * 1991-11-26 1993-06-08 Eastman Kodak Company Moisture stable biasable transfer members
US5212032A (en) * 1991-11-26 1993-05-18 Eastman Kodak Company Moisture stable polyurethane biasable transfer members
US6458919B1 (en) * 1993-02-12 2002-10-01 Ticona Gmbh Fibers made of cycloolefin copolymers
US6593452B2 (en) 1993-02-12 2003-07-15 Ticona Gmbh Fibers made of cycloolefin copolymers
US20050101761A1 (en) * 2003-11-12 2005-05-12 Lambert Timothy L. Process for removal of catalyst residues from poly-alpha-olefins
US7473815B2 (en) 2003-11-12 2009-01-06 Crompton Corporation Process for removal of catalyst residues from poly-α-olefins
US20100069687A1 (en) * 2006-09-06 2010-03-18 Chemtura Corporation Process for synthesis of polyalphaolefin and removal of residual catalyst components
EP2395028A1 (en) 2006-09-06 2011-12-14 Chemtura Corporation Process for removal of residual catalyst components
WO2011046759A1 (en) 2009-10-12 2011-04-21 Chemtura Corporation Process for synthesis of polyalphaolefin
US10562973B2 (en) 2014-04-08 2020-02-18 Prothena Bioscience Limited Blood-brain barrier shuttles containing antibodies recognizing alpha-synuclein
US20160237239A1 (en) * 2015-02-16 2016-08-18 Fina Technology, Inc. Polymer foams
US10745537B2 (en) * 2015-02-16 2020-08-18 Fina Technology, Inc. Polymer foams

Also Published As

Publication number Publication date
EP0073001A2 (de) 1983-03-02
EP0073001B1 (de) 1985-06-26
ZA826056B (en) 1983-07-27
ES515127A0 (es) 1983-10-16
AU8744682A (en) 1983-02-24
ES8308896A1 (es) 1983-10-16
AU554147B2 (en) 1986-08-07
DE3133101A1 (de) 1983-03-10
DE3264427D1 (en) 1985-08-01
CA1190347A (en) 1985-07-09
EP0073001A3 (en) 1983-05-18
AR227485A1 (es) 1982-10-29
BR8204906A (pt) 1983-08-02

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